JP2011524922A - Nanoparticulate silicone organocopolymers and their use in coatings - Google Patents

Abstract

The subject of the present invention is
B) In the presence of at least one particle P having an average diameter of 1000 nm or less, functionalized with an ethylenically unsaturated radically polymerizable group,
However, in this case B1) one or more said oxides from the group of metal oxides and metalloid oxides are used as particles P and / or B2) particles P are of the general formula [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] _m (II) wherein each group R ⁴ is independently of each other hydrogen, a hydroxy group, and optionally up to 18 C atoms each. Represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group having the following formula, where m represents an integer of 30 or more, in which case p + z = 0 with respect to at least 20 mol% of each silicone resin, 1 or 3] is used,
Obtained by radical-initiated polymerization in an aqueous medium and possibly subsequent drying of the polymer dispersion obtained in this case,
A) one or more monomers from the group comprising vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and optionally copolymerizing with these monomers A nanoparticulate silicone organocopolymer in the form of an aqueous polymer dispersion of a nanoparticulate silicone organocopolymer from possible monomers or in the form of a polymer powder dispersible in water, the said nanoparticulate silicone organocopolymer being
C) General formula R ⁹ ₃ SiO— [R ⁸ ₂ SiO _2/2 ] _n —SiR ⁹ ₃ (III) wherein the individual groups R ⁸ and R ⁹ are each independently of one another optionally substituted Optionally represents a hydroxy group, an alkyl group having up to 18 C atoms each, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group, wherein at least one of the radicals R ⁹ is a hydroxy group, an alkoxy group One or more linear polydiorganosiloxanes represented by the following formula: n represents an integer of 100 or less;
In this case B1), B2) and C), respectively formula _{^{(R 1 O) 3-k}} (R 2) k Si (CR 3 2) -X wherein, R ¹ is hydrogen, 1-6 R ² and R ³ each independently represent hydrogen, an alkyl group or aryl group having 1 to 12 carbon atoms, and k is 0, 1 or 2 can be represented, wherein X is a group having 2 to 20 hydrocarbon atoms having an ethylenically unsaturated group] and functionalized with one or more α-organosilanes It is characterized by being.

Description

  The present invention relates to nanoparticulate silicone organocopolymers in the form of aqueous dispersions or powders dispersible in water, a process for their production and in particular the use of said silicone organocopolymers in paints for the production of insulating composite systems. About.

  Insulating composite systems (WDVS) are of great importance for the insulation of buildings, especially the outer walls of buildings. WDVS typically includes a coating with an insulating material, a plaster layer, and a paint, such as a paint paint. Usual insulating materials are glass wool or polystyrene based plates. The substrate for WDVS is, for example, brick, calcareous sandstone or concrete. A plaster layer, usually based on mortar, can be applied on the insulating material. In addition, WDVS as the top layer includes a paint film. All composites consisting of building surfaces and WDVS are also referred to as thermal insulation composite facades. Building heat loss is reduced by WDVS. The insulating properties of WDVS are based on the fact that WDVS inherently contains at least one component with poor thermal conductivity, such as a component containing air pores.

  Often, damage is caused by dew during WDVS. The dew water is in the WDVS when the WDVS is cooled by ambient air, for example when the dew point of the air present in the air pores of the WDVS is achieved or below the dew point, and thus the water is cooled to a degree of condensation. Can occur. In order to evaporate the dew water generated in the WDVS and finally to release it from the WDVS, for example, when the heat carried by sunlight incident into the WDVS is no longer sufficient, the generation of dew water is especially cold. Handled with seasonal issues.

  Dew water results in a WDVS weathering test, for example, sufficient wetting of the insulating material, WDVS components, and algae growth or flaking off of the frozen dew components, so WDVS is limited in terms of insulation capacity, Damaged to the extent that they must be removed or completely repaired.

  Therefore, it is important to form the WDVS to such an extent that the collection of dew water in the WDVS or the introduction of water from the environment into the WDVS is prevented.

  In order to prevent the introduction of water into the external facade or WDVS, paints are often modified with organosilicon compounds as hydrophobic additives. That is, EP-A-0791566 recommends paints based on alkoxysilanes and possibly alkoxy-functional organopolysiloxanes for the hydrophobization of mineral building materials. German Offenlegungsschrift DE 1076946 teaches the use of organopolysiloxanes based on alkylalkoxysilanes and ethylene glycol as additives for hydrophobing porous building materials. Examples are also silicone resin paints or silicate paints or dispersion paints modified with silicone. The application of this kind of modified paint results in a coated building material, the building material surface as well as the capillaries of the building material bonded to the surface being hydrophobized. Accordingly, the correspondingly produced WDVS is surface hydrophobic and capillary hydrophobic, so that for example dew generated in the form of water vapor in WDVS is repelled by the hydrophobized coating and forms droplets. It is collected in WDVS. The water droplets have a small surface area compared to a thin water film and evaporate more slowly accordingly.

  Furthermore, capillary hydrophobic coatings form a high diffusion resistance to water vapor, thus making it difficult to release dew from the corresponding hydrophobized WDVS. In contrast, in the case of WDVS, the diffusion resistance for water vapor decreases towards the air side of the WDVS, simplifying the escape of water vapor from the WDVS.

  EP 1 833 867 describes the use of copolymers based on, for example, ethylenically unsaturated monomers and ethylenically functionalized nanoparticles as paints for building materials. However, the resulting coating is still insufficient to wet with water. Moreover, the copolymers described in the publications are not highly transparent, which represents an important requirement for paints in a number of ranges of use.

  Against this background, the use of a transparent polymer in the paint is hydrophobized to the extent that water is prevented from being introduced into the coating, and at the same time, the coating is hydrophilized to the extent that it can be wetted by water. The challenge was to provide a transparent polymer from which the applied coating was obtained.

  Surprisingly, using nanoparticulate silicone organocopolymers containing linear polydiorganosiloxane units, the hydrophilic and hydrophobic conflicting properties are required in the manner required to solve the problem according to the present invention. Can be obtained at the same time.

The subject of the present invention is
B) In the presence of at least one particle P having an average diameter of 1000 nm or less, functionalized with an ethylenically unsaturated radically polymerizable group,
However, in this case B1) one or more said oxides from the group of metal oxides and metalloid oxides are used as particles P and / or B2) particles P are of the general formula [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] _m (II) wherein each group R ⁴ is independently of each other hydrogen, a hydroxy group, and optionally up to 18 C atoms each. Represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group having the following formula, m represents an integer of 30 or more, and in this case, p + z = 0, 1, or at least 20 mol% of each silicone resin 3) is used, and
A) one or more monomers from the group comprising vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and optionally copolymerizing with these monomers Aqueous polymer of nanoparticulate silicone organocopolymers obtained from possible monomers by free radical-initiated polymerization in an aqueous medium and optionally subsequent drying of the polymer dispersion obtained in that case A nanoparticulate silicone organocopolymer in the form of a dispersion or in the form of a polymer powder redispersible in water, the nanoparticulate silicone organocopolymer
C) General formula R ⁹ ₃ SiO— [R ⁸ ₂ SiO _2/2 ] _n —SiR ⁹ ₃ (III) wherein the individual groups R ⁸ and R ⁹ are each independently of one another optionally substituted Optionally represents a hydroxy group, an alkyl group having up to 18 C atoms each, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group, wherein at least one of the radicals R ⁹ is a hydroxy group, an alkoxy group One or more linear polydiorganosiloxanes represented by the following formula: n represents an integer of 100 or less;
In this case B1), B2) and C), respectively formula _{^{(R 1 O) 3-k}} (R 2) k Si (CR 3 2) -X wherein, R ¹ is hydrogen, 1-6 R ² and R ³ each independently represent hydrogen, an alkyl group or aryl group having 1 to 12 carbon atoms, and k is 0, 1 or 2 can be represented, wherein X is a group having 2 to 20 hydrocarbon atoms having an ethylenically unsaturated group] and functionalized with one or more α-organosilanes It is characterized by being.

  Suitable vinyl esters are vinyl esters of carboxylic acids having 1 to 15 C atoms. Preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate, and in the α-position with 9-11 C atoms. Branched monocarboxylic acid vinyl esters, such as VeoVa9® or VeoVa10® (trade names of Solutions). Particularly preferred is vinyl acetate.

  Suitable monomers from the group of acrylic esters or methacrylic esters are esters of unbranched or branched alcohols having 1 to 15 C atoms. Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t -Butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.

  Preferred as the vinyl aromatic compound are styrene, α-methylstyrene, isomeric vinyl toluene and vinyl xylene and divinylbenzene. Particularly preferred is styrene.

  Vinyl halogen compounds include vinyl chloride, vinylidene chloride, tetrafluoroethylene, difluoroethylene, hexyl perfluoroethylene, 3,3,3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene and vinyl fluoride. Can be mentioned. Particularly preferred is vinyl chloride. A preferred vinyl ether is, for example, methyl vinyl ether.

  Preferred olefins are ethene, propene, 1-alkylethene and polyunsaturated alkenes, and preferred dienes are 1,3-butadiene and isoprene. Particularly preferred are ethene and 1,3-butadiene.

  As monomers A), in some cases, one or more ethylenically unsaturated monocarboxylic acids or ethylenically unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acids or their salts are in particular 0% relative to the total mass of monomer A). .1-5% by weight may be copolymerized. Preferred monocarboxylic or dicarboxylic acids are acrylic acid, methacrylic acid, fumaric acid and maleic acid. Preferred sulfonic acids are vinyl sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid. The use of ethylenically unsaturated monocarboxylic acid or ethylenically unsaturated dicarboxylic acid, or sulfonic acid results in stabilization of the aqueous dispersion or redispersion of the nanoparticulate silicone organocopolymer polymer powder.

  In some cases, 0.1 to 5% by weight of auxiliary monomers may be further copolymerized with respect to the total weight of monomer A). Advantageously, 0.5 to 2.5% by weight of auxiliary monomers are used. Examples of auxiliary monomers are ethylenically unsaturated carboxylic acid amides and ethylenically unsaturated carboxylic acid nitriles, in particular acrylamide and acrylonitrile; fumaric acid and maleic acid monoesters and diesters such as diethyl ester and diisopropyl ester and maleic anhydride. is there. Further examples are pre-crosslinkable comonomers such as polyethylenically unsaturated comonomers such as divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or postcrosslinkable comonomers such as acrylamide glycolic acid (AGA) , Methyl acrylamide glycolic acid methyl ester (MAGME), N-methylol acrylamide (NMA), N-methylol methacrylamide, N-methylol allyl carbamate, alkyl ethers such as isobutoxy ether or N-methylol acrylamide ester, N-methylol methacrylamide Ester and N-methylol allyl carbamate ester. Epoxy functional comonomers such as glycidyl methacrylate and glycidyl acrylate are also suitable. Monomers having hydroxy or CO groups, such as hydroxyalkyl methacrylates and hydroxyalkyl esters of acrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate, or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, and di- Mention may also be made of compounds such as acetone acrylamide and acetylacetoxyethyl acrylate or acetylacetoxyethyl methacrylate.

  As monomers A), vinyl acetate, α-branched monocarboxylic acids having 9 to 11 C atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, Particularly preferred are n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, and 1,3-butadiene. As monomer A) a mixture of vinyl acetate and ethylene; a mixture of vinyl acetate and ethylene and a vinyl ester of an α-branched monocarboxylic acid having 9 to 11 C atoms; n-butyl acrylate and 2- A mixture of ethyl hexyl acrylate and / or methyl methacrylate; a mixture of styrene and one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate and methyl acrylate; A mixture of one or more monomers from the group of ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; 1,3-butadiene and styrene and / or Also particularly preferred are mixtures with methyl methacrylate, in which case the mixtures described may optionally contain one or more of the above ethylenically unsaturated monocarboxylic acids or ethylenically unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acids or These salts or auxiliary monomers may further be contained.

In this case, the selection of the monomer or the mass content of the monomer is generally carried out such that a glass transition temperature of 60 ° C. or less, in particular −50 ° C. to + 60 ° C., occurs. The glass transition temperature T _g of the polymer can be calculated by differential scanning calorimetry (DSC) in a known manner. T _g can also be estimated approximately by the Fox equation. Fox T.G. Bull. Am. Physics Soc. 1, 3, page 123 (1956), the following applies: 1 / Tg = x1 / Tg1 + x2 / Tg2 +. . . + Xn / Tgn, where xn represents the mass fraction of monomer n (mass% / 100), and Tgn is the glass transition temperature at the Kelvin of the homopolymer of monomer n. The Tg value of the homopolymer was determined by Polymer Handbook 2nd Edition, J. MoI. Wiley & Sons, New York (1975).

  The proportion of monomer A) is in particular 50% by weight or more, particularly preferably 70 to 92% by weight, based on the total weight of components A), B) and C) for producing nanoparticulate silicone organocopolymers, respectively. .

  Suitable particles P are those from the group B1) of silicon oxide and metal oxide. In the case of metal oxides, metal aluminum, titanium, zirconium, tantalum, tungsten, hafnium, zinc and tin oxides are preferred. In the case of silicon oxide, colloidal silicic acid, pyrogenic silicic acid, precipitated silicic acid, and silica sol are particularly preferred. In the case of metal oxides, aluminum oxides, such as corundum, aluminum mixed oxides with other metals and / or silicon, titanium oxide, zirconium oxide, iron oxide are particularly preferred.

Preferred particles P from the group of silicone resins are at least 30 mol% composed of Q units, ie in the repeating unit [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] of the general formula (II). Particles having a meaning that p + z is 0. Particularly preferred silicone resins are composed only of M units and Q units, ie, _{p + z in} the repeating unit [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] of the general formula (II) is 0 and 3. Particles that have meaning only. When the group R ⁴ is substituted, this group additionally contains one or more selected from O, S, Si, Cl, F, Br, P or N atoms. It can contain the same or different heteroatoms. Furthermore, silicone resins comprising any combination of M units (R ³ SiO—), D units (—OSiR ² O—), T units (RSiO ₃ ³⁻ ) and Q units (SiO ₄ ⁴⁻ ) are suitable. However, it always contains T units and / or Q units, and the ratio of the T units and / or Q units to the units constituting the silicone resin is at least 20 mol% in total, If only one is present, the proportion of this unit is at least 20 mol% each.

  The most preferred silicone resin B2) is a silicone resin consisting essentially only of M and Q units, in which the molar ratio of M / Q units reaches 30/70 to 60/40, which is particularly preferred. Is a resin having an M / Q ratio of 35/65 to 45/55. Furthermore, the most preferred resins are resins which consist mostly of T units, in particular those which comprise more than 80 mol% of T units, particularly preferably resins which actually comprise 100 mol% of T units.

  In the general formula (II), m takes a value of particularly 30 to 100, particularly preferably 30 to 70, particularly preferably 30 to 50.

  The particles P preferably have an average diameter of 1-1000 nm, particularly preferably 1-100 nm, in which case the particle size is measured by transmission electron microscopy of the resulting dispersion or film obtained from the dispersion. .

  An α-organosilane is a silane in which an alkoxy-substituted, aryloxy-substituted or OH-substituted silicon atom is directly bonded to an unsaturated hydrocarbon group having one or more ethylenically unsaturated carbon bonds through a methylene bridge. In this case, the hydrogen group of the methylene bridge may be substituted by an alkyl group and / or an aryl group, and the C═C-double bond is in the α-position to the Si atom.

Also, suitable α-organosilanes of the formula (R ¹ O) _{2 -k} (R ² ) _k Si- (CR ³ ₂ ) -X (I) have carbon chains of groups R ¹ , R ² and R ^3. Organosilanes interrupted by non-adjacent oxygen, sulfur or NR ⁴ groups. Unsubstituted alkyl groups having 1 to 6 C atoms as the radicals R ¹ and R ² are preferred, and hydrogen as the radical R ³ is preferred. The group X can be linear, branched or cyclic. In addition, functional groups that are generally inert to olefin polymerizations, such as halogen groups, carboxy groups, sulfinate groups, sulfonate groups, amino groups, azide groups, nitro groups, epoxy groups, alcohol groups, ethers, together with double bonds. Groups, ester groups, thioether groups and thioester groups and aromatic isocyclic groups and heterocyclic groups may be present. Preferred examples of X are monounsaturated C _{2 to} C ₁₀ groups, and most preferred are the group X as an acryl group and a methacryl group.

Along with functionalization with α-organosilane, γ-organosilane (silicon atom is bonded to unsaturated hydrocarbon group by one propylene bridge) or vinylorganosilane H ₂ C═CH—SiX ₃ (this In this case it is pointed out that component B), which is functionalized with X) independently of one another, is an alkyl or alkoxy group, is also suitable.

  The proportion of monomer B) is in particular from 0.5 to 49.9% by weight, preferably from 1 to 4%, based on the total weight of components A), B) and C) for producing nanoparticulate silicone organocopolymers, respectively. 30% by weight, particularly preferably 4 to 20% by weight.

Examples of preferred linear polydiorganosiloxanes C) are linear monofunctional silicone oils of the general formula R ⁹ ₃ SiO— [R ⁸ ₂ SiO _2/2 ] _n —SiR ⁹ ₃ , in this case the group R ⁸ is bonded to each silicon atom of the siloxane chain by one carbon atom each, and one of the two terminal silicon atoms of the siloxane chain is three groups R ⁹ bonded by one carbon atom. has another terminal silicon atoms have one one radical R ⁹ joined by two groups R ⁹ and one carbon atom bonded by a carbon atom, in this case A hydroxy group, an alkoxy group or an aryloxy having the ability to react with an α-organosilane of the general formula (R ¹ O) _3k (R ² ) _k Si— (CR ³ ₂ ) —X (I) as described above The group is a problem.

  For the functionalization of linear polydiorganosiloxanes C), the same organosilanes described correspondingly for component B) are suitable or preferred.

  In the formula III, n is an integer from 1 to 40, particularly preferably from 1 to 25, particularly preferably from 1 to 10.

In the formula III, the radical R ⁸ represents in particular methyl, phenyl or hydrogen, particularly preferably methyl. The group R ⁹ is in particular selected from the group comprising methyl, phenyl, hydrogen, methyloxy, phenyloxy and hydroxy, particularly preferably from the group comprising methyl and methyloxy.

Examples of preferred polydiorganosiloxanes C) which are functionalized with α-organosilanes are in particular values n ( ¹ H-NMR spectroscopy) of 1 to 60, particularly preferably 1 to 40, particularly preferably 1 to 20. Α-methacryloxymethyl polydimethylsiloxane and α-methacryloxypropyl polydimethylsiloxane having (measured by 1).

  The proportion of polydiorganosiloxane C) is preferably 0.1 to 10% by weight, particularly preferably 0, based on the total weight of components A), B) and C), respectively, for the production of nanoparticulate silicone organocopolymers. 0.1 to 7% by weight, particularly preferably 0.1 to 5% by weight.

Components A), B) and C) together with the nanoparticulate silicone organo copolymer, component A), B) and C) the general formula relative to the total weight of _{^{(R 5) 4-j -Si-}} (OR 6) at least one silane represented by _j (IV) can still be contained up to 30% by weight, wherein j represents one number of values 1, 2, 3 or 4 and R ⁵ Are each an alkoxy group having 1 to 12 C atoms and an aryloxy group, phosphonic acid monoester group, phosphonic acid diester group, phosphonic acid group, methacryloyloxy group, acryloyloxy group, vinyl group, mercapto group, isocyanato group However, in this case, the isocyanato group may optionally be blocked for protection from chemical reaction, and may be a hydroxy group, a hydroxyalkyl group, a vinyl group, An epoxy group, a glycidyloxy group, a morpholino group, a piperazino group, a primary amino group, a secondary amino group or a tertiary amino group having one or more nitrogen atoms, where the nitrogen atom is hydrogen or a monovalent aromatic An organic functional group selected from the group consisting of a carboxylic acid group, a carboxylic anhydride group, an aldehyde group, a urethane group, and a urea group, which may be substituted by an aliphatic, aliphatic or alicyclic hydrocarbon group, In this case, the radical R ⁵ may be directly bonded to the silicon atom or may be separated from the silicon atom by a carbon chain of 1 to 6 C atoms, each R ⁶ being 1 to 12 Represents a monovalent linear or branched aliphatic or alicyclic hydrocarbon group or monovalent aromatic hydrocarbon group having a C atom, or the group -C (= O) -R ⁷ is represents, in this case R ⁷ is, it It represents a monovalent straight or branched aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon radical having 1 to 12 C atoms. The selected silane or optionally the selected silane is in an unhydrolyzed form, hydrolyzed form or hydrolyzed and partially condensed form or hydrolyzed and condensed form, or It can exist in a mixed form.

  The average diameter of the particle domains in the nanoparticulate silicone organocopolymer is in particular in the range from 1 nm to 1000 nm, in particular from 1 nm to 500 nm, particularly preferably from 1 nm to 200 nm. This average diameter can be measured, for example, by manual scanning electron microscopy or transmission electron microscopy of an aqueous dispersion or polymer film of nanoparticulate silicone organocopolymer.

  Furthermore, in the case of miniemulsion polymerization, in some cases the hydrophobic additive may still be present in an amount of up to 3% by weight, based on the total weight of components A), B) and C) (so-called “ Co-surfactant "," hydrophobizing agent "). In the case of the present invention, the silicone particles can often inherit the function of a “cosurfactant”. Further examples of co-surfactants are hexadecane, cetyl alcohol, paraffin, oligomeric cyclosiloxanes such as octamethylcyclotetrasiloxane, but also vegetable oils such as rapeseed oil, sunflower oil or olive oil. Furthermore, organic or inorganic polymers having a number average molecular weight of less than 10,000 are suitable. According to the invention, preferred hydrophobizing agents are the silicone particles to be polymerized themselves, as well as D3 cyclic compounds, D4 cyclic compounds and D5 cyclic compounds, and hexadecane. Particularly preferred are silicone particles, paraffin and hexadecane to be polymerized.

  Copolymers are produced by known techniques of suspension polymerization, emulsion polymerization or miniemulsion polymerization in a heterophasic process (eg Peter A. Lovell, MS El-Aasser, "Emulsion Polymerization and Emulsion Polymers" 1997, John Wiley and Sons, See Chichester). This reaction is carried out in a particularly preferred manner by the method of miniemulsion polymerization. Miniemulsion polymerization is distinguished from other heterophasic polymerizations by some essential points that water-insoluble monomers are particularly suitable for copolymerization (eg, K. Lnadfester, "Polyreactions in Miniemulsions", Macromol. Rapid Commun. 2001, 22, 896-936 and MS El-Aasser, ED Sudol, "Miniemulsions: Overview of Research and Applications" 2004, JCT Research, 1, 20-31).

  The reaction temperature is 0 ° C. to 100 ° C., preferably 5 ° C. to 80 ° C., particularly preferably 30 ° C. to 70 ° C. The pH value of the dispersion medium is 2-9, preferably 4-8. In a particularly preferred embodiment, it is 6.5 to 7.5. The pH value before the start of the reaction can be adjusted with hydrochloric acid or caustic soda solution. The polymerization is carried out by the metering method with the charging of all or individual components of the reaction mixture, or with partial and post-metering of individual components of the reaction mixture or without charging. be able to. All metering takes place in particular according to the amount of each component used.

The polymerization is initiated by a conventional water soluble initiator or by a combination of redox initiators. Examples of initiators are sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, potassium peroxodiphosphate, tert-butyl peroxopivalate, cumene hydroperoxide Isopropylbenzene monohydroperoxide and azobisisobutyronitrile. The described initiators are used in particular in an amount of 0.01 to 4.0% by weight, based on the total weight of the monomers. As a combination of redox initiators, the above initiators are used together with one reducing agent. Suitable reducing agents are monovalent cation sulfites and bisulfites, such as sodium sulfite, derivatives of sulfoxylic acid, such as zinc formaldehyde sulfoxylate or alkali metal formaldehyde sulfoxylate, such as sodium hydroxymethanesulfinate and ascorbic acid. It is. The amount of the reducing agent is 0.15 to 3% by mass with respect to the amount of monomer used. Additionally, a small amount of metal compound that is soluble in the polymerization medium may be introduced, and the metal component of this metal compound is redox active, for example against iron or vanadium, under polymerization conditions. A particularly preferred initiator system from the above components is tert-butyl hydroperoxide / tert-butyl sodium hydroxymethane sulfinate / Fe system (EDTA) ^{2 + / 3 +} .

  In the case of carrying out the reaction by means of a miniemulsion polymerization process, mainly oil-soluble initiators such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide or azobisisobutyronitrile may be used. Preferred initiators for the miniemulsion polymerization process are potassium persulfate, ammonium persulfate, azobisisobutyronitrile and dibenzoyl peroxide.

  In order to produce a nanoparticulate silicone organocopolymer in the form of a redispersible polymer powder in water, the aqueous dispersion of nanoparticulate silicone organocopolymer is dried by methods known to those skilled in the art, in particular by spray drying. The

  Furthermore, the subject of the present invention is a paint containing one or more nanoparticulate silicone organocopolymers according to the invention and optionally one or more auxiliaries and optionally one or more additives.

  Examples of auxiliaries are surfactants, in which case anionic surfactants as well as nonionic surfactants or cationic surfactants or amphoteric surfactants are suitable. In addition, the auxiliaries are pigments such as soil pigments such as chalk, yellow earth, amber, green earth, mineral pigments such as titanium dioxide, chrome yellow, red lead, zinc yellow, zinc green, cadmium red, cobalt blue. Organic pigments such as sepia, Kasseler Braun, indigo, azo pigments, anthraquinoid pigments, indigoid pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments and alkali blue pigments.

  Additives are, for example, biocides, thickeners, alkyl orthotitanates, alkyl borate esters, pigment wetting agents and dispersants, antifoaming agents, anticorrosive pigments, metal oxides, metal carbonates or organic resins.

  The paint is a nanoparticulate silicone organocopolymer dispersion, in particular 1-90% by weight, particularly preferably 4-70% by weight; a surfactant, in particular 0.1-10% by weight, particularly preferably 0.5-5% by weight. Pigments, in particular 0.5 to 40% by weight, particularly preferably 2 to 35% by weight, particularly preferably 5 to 30% by weight; additives, in particular 0.1 to 60% by weight, particularly preferably 1 to 50% by weight, Particularly preferably 10 to 40% by weight; water, in particular 10 to 70% by weight, particularly preferably 15 to 65% by weight, particularly preferably 20 to 60% by weight. In this case, the proportion in mass% is relative to the total mass of the respective paint.

  For the production of the paint, the individual components of the paint can be mixed in conventional equipment for this in any way. In particular, the nanoparticulate silicone organocopolymer is added to the paint in the form of a powder, as is typical for silicone resin binders, or to the paint during application in the form of a dispersion.

  In particular, this paint is used to paint and apply to buildings, for example in the interior or especially in the exterior, or else as a paint on the veranda or terrace.

  However, the paint may also be used to apply unattached building materials such as bricks, calcareous sandstone or concrete blocks.

  The paint containing the paint according to the present invention may be blended with supercriticality or with subcriticality. Preference is given to supercritical formulations, ie paints having a pigment volume concentration (PVK) greater than 60%. The definition of the pigment volume concentration is known to those skilled in the art from the description of Ullmanns Enzyklopaedie der technischen Chemie, 4th edition, volume 15, page 668, for example.

  Further, the subject of the present invention is an insulating material containing a thermal insulating composite system (WDVS) and one or more coatings, one coating for forming at least one of the coatings. It is characterized by the use of the coating material containing the above nanoparticulate silicone organocopolymer according to the present invention.

  Suitable insulating materials are, for example, mineral cotton, such as rock wool or glass wool, mineral foam, such as calcium silicate hydrate, organic materials or synthetic materials, such as polystyrene rigid foam (PS), polystyrene particle foam (EPS), polystyrene Extruder foam (XPS), polyurethane rigid foam (PUR), vacuum insulation board (VIP), or natural materials such as wood fiber, cork, cannabis or straw.

  The coating can include one or more plaster layers, such as a primer plaster, optionally containing a woven fabric, and optionally a finish plaster. In particular, the plaster layer is based on mortar.

  WDVS can be manufactured by conventional methods and may be applied to all normal platforms. Typically, the insulating material is applied to each subsurface by means of an adhesive, screws or nails in the form of a board or sheet. Typical substrates are natural minerals, metals, plastics or natural materials such as wood or wood plastic composites. A preferred substrate is brick, calcareous sandstone or concrete. One or more plaster layers may be applied over the insulating material. A paint containing one or more nanoparticulate silicone organocopolymers according to the present invention is applied on WDVS, in particular as the top layer. In this case, the paint according to the invention is particularly preferably a paint.

  The WDVS according to the invention is particularly suitable for outer building surfaces, particularly preferably for building outer walls.

  Preferably, the paint according to the invention produces a porous vapor-permeable coating, in which water decomposes on the surface of the coating or in the capillary of the coating and does not flow as polka dots, in this case the coating Is sufficiently hydrophobic to prevent liquid water from entering the coating or WDVS from the outside.

  Along with the above applications, the silicone organocopolymers according to the invention are used for the production of coating materials or impregnations and coatings obtained therefrom and substrates, such as metals, glass, wood, mineral substrates, textiles, carpets, floor coverings, or It may be used in the production of plastic fibers and natural fibers, leather, plastics such as sheets, covers on molded bodies for the production of other objects that can be produced from fibers. The silicone organocopolymers according to the present invention may be incorporated into elastomeric materials in liquid or cured solid form. In this case, the silicone organocopolymer can be used to enhance or improve other usage characteristics, such as control of transparency, thermal stability, tendency to yellowing, weather resistance. Silicone organocopolymers can be used as pure substances for the stated purposes, i.e. without other additives.

  Nanoparticulate silicone organocopolymers have high storage stability. This nanoparticulate silicone organocopolymer gives the coating significant resistance to, for example, climatic influences, chemical attack and UV radiation. Similarly, this coating provides very good water resistance and a low tendency to contamination. By introducing a silane containing hydrolyzable and condensable groups into the silicone organocopolymer, it is possible to produce a paint that is moisture curable after application of the paint, thus coating hardness, thermoplasticity And the pollution tendency can be adjusted.

  All descriptions are at room temperature and normal pressure unless otherwise noted.

Production of methacrylic functional particles Particle 1:
A solution comprising 100 parts by mass of particulate organopolysiloxane resin in toluene (39% M units; 61% Q units; R ⁴ as described in formula II: methyl) and 5 parts by mass of α-silane methacrylatomethyl-methyldimethoxysilane Was reacted in the presence of 3 parts by weight of an acidic catalyst Tonsil® Optimum FF (acidic layered silicate; trade name of Sued-Chemie). After filtering off the catalyst, the solvent was evaporated.

Production of nanoparticulate silicone organocopolymer:
Example 1: Polymer 1:
6560 g of water was supplied to a 100 liter reaction kettle equipped with a jacket cooling section, an evaporative cooling section, and a horseshoe stirrer, and 1 gram of Fe (II) -EDTA complex was added. The device was defeated automatically by evacuating the vacuum twice with nitrogen. In the second kettle, methacrylic acid, water and sodium dodecyl sulfate were dissolved in the amounts described in the metering 1 item below (aqueous phase).

  In the third kettle, the remaining components of the metering supply 1 item were uniformly dissolved in the above amount (oil phase). Subsequently, this oil phase was introduced into a kettle having an aqueous phase with thorough stirring. The crude emulsion thus obtained was homogenized in one pass with an IKA high-pressure homogenizer at a pressure of 800 bar. A pre-emulsion containing all the components of the metering 1 item was obtained. This pre-emulsion was stirred at room temperature in a stirring pot (pre-emulsion pot). In each separate kettle, the components of metering item 2 or the components of metering item 3 were introduced in the amounts described below.

Metering supply 1 (all in grams):
Hexadecane 131.2
Butyl acrylate 7216
Methyl methacrylate (MMA) 6560
Butyl methacrylate 2296
Styrene 1312
Methacrylic acid 360.8
Sodium dodecyl sulfate 492
Linear monomethacrylatomethyl functional PDMS (number average molecular weight: 1200 g / mol) 918.4
Particle 1 918.4
Distilled water 9840
Metering supply 2 (all in grams):
Water 1417
Tertiary butyl hydroperoxide 157.4
Metering supply 3 (all in grams):
Water 1496
Brueggolit® 78.7.

  The reaction kettle supplied with water was heated to 50 ° C. The reaction was started by simultaneous start of metering 1-3. The components of metering item 1 were fed into the reaction kettle over 3 hours, while the components of metering items 2 and 3 were metered over a time of 200 minutes. In this case, the reaction mixture was maintained at a temperature of 50 ° C. by jacket cooling of the reaction kettle. After complete addition of the individual metering item components, stirring was still continued for 30 minutes. Subsequently, a 10% by weight aqueous ammonia solution was used to bring the pH value of the dispersion to a pH value of about 3 to 8.0. After the dispersion thus obtained was filtered through a screen stocking having an opening of 50 micrometers, the dispersion was obtained with a solid content of 50% and a volume average particle size of 90 nm.

Example 2: Polymer 2:
Production of polymer 2 was carried out as in Example 1, but “metering 1” had the following composition:
Metering supply 1 (all in grams):
Hexadecane 131.2
Butyl acrylate 7216
MMA 7872
Butyl methacrylate 2296
Methacrylic acid 360.8
Sodium dodecyl sulfate 492
Linear monomethacrylatomethyl functional PDMS (number average molecular weight: 1200 g / mol) 918.4
Particle 1 918.4
Distilled water 9840
Polymer 3:
The production of polymer 3 was carried out in accordance with Example 1, but “metering 1” had the following composition:
Metering supply 1 (all in grams):
Hexadecane 131.2
Butyl acrylate 7216
MMA 6560
Butyl methacrylate 2296
Styrene 1312
Methacrylic acid 360.8
Sodium dodecyl sulfate 492
Particle 1 1837
Distilled water 9840
Polymer 4:
The production of polymer 4 was carried out in accordance with Example 1, but “metering 1” had the following composition:
Metering supply 1 (all in grams):
Hexadecane 131.2
Butyl acrylate 7216
MMA 6560
Butyl methacrylate 2296
Styrene 1312
Methacrylic acid 360.8
Sodium dodecyl sulfate 492
Linear monomethacrylic functional PDMS 1837 having a number average molecular weight of about 1200 g / mol
Distilled water 9840.

  All polymers were obtained in the form of dispersions having a solids content FG of about 50% by weight, a volume average particle size of about 90 nm and a pH value of 8.0.

Paint production:
Each paint was prepared by sequentially adding the components listed in Table 1 according to the numbering and mixing thoroughly using a conventional high speed stirrer (Getzmann Dissolver). .

Coating Performance Test In the following (comparative) examples, all parts by weight or weight percent relate to the total weight of the respective composition unless otherwise stated.

According to DIN EN 1062-3, each test specimen was coated with the respective paint (Table 1) on the calcareous sandstone with a coating thickness of 200 g / m ² using a brush, and the calcareous sandstone thus coated was applied. Prepared by drying for 1 week at room temperature and then storing for 24 hours in a standard air-conditioned room (23 ° C. ± 2 ° C., 50% ± 5% relative air humidity).

The water permeability of each specimen was measured according to DIN EN 1062-3 (Measurement of water permeability of coating film, February 1999). The uncoated calcareous sandstone had a water absorption coefficient of 6.19 kg / (m ² h ^0.5 ) after 24 hours of water storage W ₂₄ . The water absorption values thus obtained are listed in Table 2.

  The water vapor transmission rate was measured for each specimen according to ISO 7783-2 (see Table 2).

  The water absorption rate of each test was measured according to DIN EN 1062-3, but the test specimens were stored in fresh tap water 3 times every 24 hours and not dried for 72 hours each. And then dried in water at 50 ° C. ± 5 ° C. for 24 hours. The water absorption values thus obtained are listed in Table 2.

  In order to evaluate the surface hydrophobicity, the beading effect was measured (Table 2). To that end, water droplets were brought on the test specimens stored in the horizontal direction. It was observed whether the water droplets flowed in as polka dots, stayed on the surface, decomposed, or penetrated.

This beading effect was evaluated for the school-grade system according to the following evaluation criteria:
1 = very good beading effect, no wetting of the substrate, water flows completely as polka dots, no droplets adhere.
2 = good beading effect, individual water droplets are attached, but no water penetration.
3 = reasonable beading effect, the substrate is partially wet.
4 = poor beading effect, the substrate is wet.
5 = No beading effect, the substrate is wet and colored darkly by absorbed water.
For the measurement of transparency, an aqueous dispersion of the respective polymer having a solids content FG of 50% by weight was produced. Each dispersion was drawn into a film using a four-sided coating bar (Kastenrakel) with a gap width of 100 micrometers and dried at room temperature for 24 hours. Subsequently, in relation to DIN 50014, the film is evaluated on a scale of 1 to 10 by visual testing, where 1 corresponds to a completely transparent film and 10 corresponds to an opaque film.

a) The silicone resin paint has a composition corresponding to Table 1, in which the silicone resin emulsion of methyl silicone resin (molecular weight Mw of 6000 g / mol; all hydrocarbon groups directly bonded to silicon are used as binders) Methyl silicone resin is 0.4% hydroxy groups and 3.7% ethoxy groups based on the total mass of the particles and a silicone-containing early hydrophobizing additive (α in the presence of KOH). , ω-bishydroxy-polydimethylsiloxane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane condensation product aqueous emulsion (FG = 55%) silicone-containing early hydrophobizing additive is about 0.3 an amine value, viscosity and N-(2-aminoethyl) about 1500 mm ² / s at 25 ° C. 3- aminopropyl trimetrexate Having a residual methoxy content of less than 5 mol% with respect to methoxy groups initially present in Shishiran.) And Wacker Polymer Systems, Inc. of Flexcryl SAF 34 (dispersing binder) is contained.

  The coating containing the standard silicone resin paint (Table 2: Comparative Example 8) has very little water vapor permeability and low water absorption, and shows a markedly beading effect, which means that the external facade Cause the problems mentioned at the beginning in the corresponding use of the coating in Moreover, the coating film of the comparative example 6 or 7 (polymer 3 or 4) shows a remarkable beading effect. Only Example 4 or 5 according to the present invention containing the silicone organocopolymer according to the present invention exhibits good water absorption and water vapor permeability, and at the same time hydrophilic so that water droplets penetrate the surface and do not flow as polka dots. is there. Furthermore, the silicone organocopolymer according to the invention (polymer 1 or 2) is more transparent than the polymer 3 or 4 used in comparative example 6 or 7.

Claims (13)

B) In the presence of at least one particle P having an average diameter of 1000 nm or less, functionalized with an ethylenically unsaturated radically polymerizable group,
However, in this case B1) one or more said oxides from the group of metal oxides and metalloid oxides are used as particles P and / or B2) particles P are of the general formula [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] _m (II) wherein each group R ⁴ is independently of each other hydrogen, a hydroxy group, and optionally up to 18 C atoms each. Represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group having the following formula, where m represents an integer of 30 or more, in which case p + z = 0 with respect to at least 20 mol% of each silicone resin, 1 or 3] is used,
Obtained by polymerization initiated by free radicals in an aqueous medium and in some cases subsequent drying of the polymer dispersion obtained in this case,
A) one or more monomers from the group comprising vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and optionally copolymerizing with these monomers In a nanoparticulate silicone organocopolymer in the form of an aqueous polymer dispersion of nanoparticulate silicone organocopolymer from possible monomers or in the form of a polymer powder dispersible in water,
C) General formula R ⁹ ₃ SiO— [R ⁸ ₂ SiO _2/2 ] _n —SiR ⁹ ₃ (III) wherein the individual groups R ⁸ and R ⁹ are each independently of one another optionally substituted Optionally represents a hydroxy group, an alkyl group having up to 18 C atoms each, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group, wherein at least one of the radicals R ⁹ is a hydroxy group, an alkoxy group One or more linear polydiorganosiloxanes represented by the following formula: n represents an integer of 100 or less;
In this case B1), B2) and C), respectively formula _{^{(R 1 O) 3-k}} (R 2) k Si (CR 3 2) -X wherein, R ¹ is hydrogen, 1-6 R ² and R ³ each independently represent hydrogen, an alkyl group or aryl group having 1 to 12 carbon atoms, and k is 0, 1 or 2 can be represented, wherein X is a group having 2 to 20 hydrocarbon atoms having an ethylenically unsaturated group] and functionalized with one or more α-organosilanes Nanoparticulate silicone organocopolymer in the form of an aqueous polymer dispersion of nanoparticulate silicone organocopolymer or in the form of a polymer powder dispersible in water. Groups R ⁸ linear polydiorganosiloxanes C) are methyl, phenyl or hydrogen, according to claim 1 nanoparticulate silicone organo copolymer according. Group R ⁹ linear polydiorganosiloxanes C) are methyl, phenyl, hydrogen, methyloxy, is selected from the group comprising phenyl oxy or hydroxy, claim 1 or 2 nanoparticulate silicone organo copolymer according.   4. The oxide according to claim 1, wherein the particles P from the group B1 are silicon oxide or an oxide of the metals aluminum, titanium, zirconium, tantalum, tungsten, hafnium, zinc or tin. Nanoparticulate silicone organocopolymer. For the particles P from group B2), a silicone resin of the general formula [R ⁴ _{(p + z)} SiO _{(4-pz) / 2} ] _m (II) is used. R ³ SiO—), D units (—OSiR ² O—), T units (RSiO ₃ ³⁻ ), and Q units (SiO ₄ ⁴⁻ ) in any combination, provided that in this case always T units and / or When the Q unit is contained, the ratio of the T unit and / or the Q unit to the unit constituting the silicone resin is at least 20 mol% in total, and when only one of the units is present, The nanoparticulate silicone organocopolymer according to any one of claims 1 to 3, wherein the proportion of these units is at least 20 mol% each. Unsubstituted wherein the α-organosilane of the formula (R ¹ O) _{3 -k} (R ² ) _k Si- (CR ³ ₂ ) -X (I) has ^{1 to} 6 C atoms as radicals R ¹ and R ² The nanoparticulate silicone organocopolymer according to any one of claims 1 to 5, having the following alkyl: hydrogen as group R ^{3 and} monounsaturated C ₂ -C ₁₀ group as group X .   The nanoparticulate silicone organocopolymer according to any one of claims 1 to 6, wherein the average diameter of the particle domain of the nanoparticulate silicone organocopolymer is 1 nm to 1000 nm.   The method for producing a nanoparticulate silicone organocopolymer according to any one of claims 1 to 7, by suspension polymerization, emulsion polymerization or miniemulsion polymerization.   8. A paint comprising one or more nanoparticulate silicone organocopolymers according to any one of claims 1 to 7 and optionally one or more auxiliaries and optionally one or more additives.   Use of paint according to claim 9 in paint.   8. In a thermally insulating composite system (WDVS) comprising an insulating material and one or more coatings, one or more of any one of claims 1 to 7 for forming at least one of the coatings. Insulating composite system (WDVS) comprising an insulating material and one or more coatings, characterized in that a coating containing a nanoparticulate silicone organocopolymer is used.   8. Any of claims 1 to 7 for the production of paint materials and impregnations and for the production of textiles, carpets, floor coverings or other objects, leathers, plastics, eg sheets, molded bodies that can be produced from fibers. Use of the nanoparticulate silicone organocopolymer according to item 1.   Use of the nanoparticulate silicone organocopolymer according to any one of claims 1 to 7 for incorporation into an elastomeric material.